CN108350583A - By the power cable for the aluminium that tetrazole compound corrosion inhibitor coats - Google Patents
By the power cable for the aluminium that tetrazole compound corrosion inhibitor coats Download PDFInfo
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- CN108350583A CN108350583A CN201580083236.9A CN201580083236A CN108350583A CN 108350583 A CN108350583 A CN 108350583A CN 201580083236 A CN201580083236 A CN 201580083236A CN 108350583 A CN108350583 A CN 108350583A
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- corrosion inhibitor
- power cable
- tetrazole
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/2806—Protection against damage caused by corrosion
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B7/00—Insulated conductors or cables characterised by their form
- H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
- H01B7/28—Protection against damage caused by moisture, corrosion, chemical attack or weather
- H01B7/282—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
- H01B7/2825—Preventing penetration of fluid, e.g. water or humidity, into conductor or cable using a water impermeable sheath
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/185—Substances or derivates of cellulose
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
- H01B3/305—Polyamides or polyesteramides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
- H01B3/421—Polyesters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/14—Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Insulated Conductors (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
Abstract
The present invention relates to a kind of power cables, it includes the metal electrical conductor surrounded by one or more layers semiconductive layer and one or more layers insulating layer, the cable has at least one hardware made of aluminum, being in direct contact for corrosion inhibitor and at least one hardware made of aluminum is wherein provided, and the wherein described corrosion inhibitor is the corrosion inhibitor of formula (I).
Description
Invention field
The present invention relates to the cables for power transmission/distribution.Particularly, the present invention relates to containing at least one aluminium element
Power cable.
Background of invention
Power cable can be used for the transmission or distribution of both direct current (DC) or alternating current (AC).
Cable for power transmission/distribution under middle pressure (MV) or high pressure (HV) is typically provided with containing metal electrical conductor
The cable core of (usual aluminium or copper), the cable core is from radially innermost layer to radially layer by internal semiconductive layer and insulating layer packet
It encloses.Cable core is further surrounded by external semiconductive layer, metal screen layer (screen) (usual aluminium or copper) and epitheca.
In the description of the invention, the use of term " middle pressure " refer to typically from about 1kV to the voltage of about 30kV and art
Language " high pressure " refers to the voltage higher than 30kV.
The advantages of aluminium is lighter than copper and cheap, but in the presence of water moisture, it is easy to aoxidize and corrode, therefore containing aluminium member
The cable of part should have moisture or barrier, to prevent water from permeating and reach aluminium element.
As moisture or barrier, the longitudinal sealing sheet material that core provides metal or plastic/metal layered product can be surrounded.Gold
Category can be aluminium.In the case of layered product, plastic layer is facing generally towards the external jacket (jacket) of cable and contacts and puts
It sets.
Because water contact cable core causes to may occur in which various problems, then water penetration to stagnated in cable and in it be should
The event avoided.After the fabrication, cable is usually stored and is transported using protection cap on its head.
However, although above-mentioned precautionary measures, but still may alternatively appear in the infiltration and stagnation of water in cable core.Particularly, exist
For example because of the negligence of installation personnel during installation, and because in the case where cable aluminium parts are exposed to environment, power cable
Any defect in polymer sheath leads to the infiltration and stagnation that can not possibly exclude water.
The component involved in etching problem depends on type of cable.Non-exhaustive list may include cable (screen
Wire), equalizing strip (equalizing tape), barrier, sheet material etc..
In the presence of water, it is known that aluminium forms stable protective oxide film (referring to example within the scope of about 4 to 8 wide pH
Such as Aluminium Corrosion, UK Aluminium Industry Fact Sheet 2, ALFED,www.alfed.org.uk)。
According to the report of Khaled et al. the, " inhibitory effect that some terazole derivatives corrode Al in acid solution:Change
It learns, electrochemistry and theoretical research (The inhibitive effect of some tetrazole derivatives
towards Al corrosion in acid solut ion:Chemical,electrochemical and
Theoretical studies) ", Materials Chemistry and Physics, 113,2009, the 150-158 pages, aluminium
Protective oxide film be both sexes and substantially dissolved when metal is exposed under the acid or alkali of high concentration.In these environment
In should use corrosion inhibitor because in 4 to 8 pH range above and below, the solubility of oxidation film increases and aluminium is shown
Go out uniform attack.Dissolving metal is prevented using inhibitor.
Khaled et al. is related to the terazole derivatives in various concentration, that is, 1- phenyl -1H-TETRAZOLE -5- mercaptan (A), 1-
Phenyl -1H-TETRAZOLE (B), 1H-TETRAZOLE -5- amine (C), 1H-TETRAZOLE (D) exist in the absence of, the aluminium in 1.0M hydrochloric acid solutions
Corrosion inhibits.The reduction of aluminium dissolving is attributed in the mercapto found in compound A in the presence of the compound of these tests
Existing sulphur atom and the ring for being attributed to amino and heterocycle.
Tetrazole compound is reported in other documents and patent references to other non-ferrous metals, for example, silver and
The corrosion of copper is inhibited.
Especially F.Zucchi et al., " corrosion inhibitor (Tetrazole of the terazole derivatives as copper in chloride solution
Derivatives as Corrosion Inhibi tors for Copper in Chloride Solutions) ",
Corrosion Science, volume 38, o. 11th, 2019-2029, page 1996 are related to some terazole derivatives in chlorination
The inhibiting effect of copper corrosion in object solution.In the derivative tested, 5- phenyl-tetrazolium (5Ph-T) and 5- sulfydryl -1- benzene
Base-tetrazolium (5Mc-1Ph-T) reduces their rejection ability at 80 DEG C.The conductance data that polarize proof is at 40 DEG C, only
5Mc-1Ph-T can maintain its protection feature almost 60'.
US 5,744,069 is related to a kind of water-soluble metal corrosion inhibitor, it includes being used for non-ferrous metal, such as copper,
Certain tetrazole compounds of copper alloy and superhard alloy.Indicate that the water-soluble metal containing tetrazole compound is anticorrosive with following formula (A)
Agent：
Wherein R1 and R2 respectively indicate hydrogen, the alkyl with 1-20 carbon atom, naphthenic base, phenyl, alkyl phenyl, ammonia
Base, sulfydryl or alkyl thiol.
US 4,873,139 is related to assigning these by making silver and copper surface contact with 1- phenyl -1H-TETRAZOLE -5- mercaptan
The technology of surface erosion resistance.
Invention description
Applicant have observed that in cable application, or even may occur in which aluminium within the scope of above-mentioned 4 to 8 pH
Corrosion phenomenon.Particularly, applicant have observed that these corrosion phenomenons equally seriously endanger the integrality of aluminium component.In addition, removing
Other than the function of sacrificing power cable, dangerous situation can be led to because aluminium corrosion causes to release hydrogen.
In the case where being not wishing to be bound by theory, applicants assume that this corrosion phenomenon of aluminium may be mainly due to because of electricity
Three kinds of redox mechanisms caused by the special tectonic of power cable cause.
This redox mechanism is (i) in water penetration, the on aluminum surfaces oxidation-of the interface of air/water
Reduction reaction, (ii) is because of aluminium and carbon black from adjacent semiconductive layer or caused by loading being electrically coupled between the water sucting belt of carbon black
Oxidation-reduction reaction, wherein aluminium work as sacrificial anode, and (iii) oxidation-caused by being electrically coupled between aluminium and copper
Reduction reaction, wherein aluminium remain as sacrificial anode and equally work.
Applicant have observed that in the case of being created substantially absent oxygen in cable, it is impossible to obtain the protection of aluminium oxide
Layer is sufficiently formed.
In face of avoiding in power cable, what aluminium corrosion inhibited especially within the scope of above-mentioned 4 to 8 pH asks applicant
Topic.
Furthermore, it is contemplated that the operating condition of power cable, the suitable inhibitors that aluminium corrodes in power cable should be through prolonging
Long period (order of magnitude be at least several months) and play its function at a temperature of more than 30 DEG C.
Summary of the invention
It has been found by the applicant that can be solved the above problems by power cable of the offer comprising aluminium component and corrosion inhibitor,
The corrosion inhibitor is in direct contact with aluminium component, which has at least one hydroxyl for being connected to cyclophane race component part
Base-tetrazolium component part.
Possible theoretical explanation is, although hydroxy-tetrazole component part seems to be suitable for interacting with metallic aluminium, ring
Aromatic group can provide the hydrophobic protective to water.The combination of the two component parts can be delayed period and be noticeably greater than
The compound that formula (I) is assigned at a temperature of room temperature is suitable for protecting the corrosion inhibiting ability of the aluminium parts of power cable.
Therefore, in the first aspect, the present invention relates to the power cables for including hardware made of aluminum, wherein corroding
Inhibitor is in direct contact with hardware and is provided, which has logical formula (I)：
R1-Ar-R2 (I)
Wherein R1 is 1- hydroxy-tetrazole -5- bases, 2- hydroxy-tetrazole -5- bases, 1- acryloxies-tetrazolium -5- bases or 1-
(2- carboxy vinyls)-tetrazolium -5- bases；
Ar is monocycle or bicyclic aromatic component part；With
R2 is hydrogen atom (H) or 1- hydroxy-tetrazole -5- bases, 2- hydroxy-tetrazole -5- bases, hydroxyl (OH), vinyl, allyl
Base or-O-CO-R4 bases, wherein R4 are the alkenyls for having 2-6 carbon atom.
When Ar is that monocyclic aromatic component part and R2 are different from hydrogen atom, R1 and R2 relative to each other, o-, m- or p-
In position.
When Ar is bicyclic aromatic component part and R2 is different from hydrogen atom, R1 and R2 relative to each other can be in peri positions
(peri position), or preferably can be the substituent group of identical ring.
Ar is advantageously selected from benzene and naphthalene component part.
Preferably, the corrosion inhibitor for being used for cable of the present invention has the following general formula (Ia)
Wherein R1 and R2 has and the identical meanings defined in the above formula (I).
Preferably, R1 is 1- hydroxy-tetrazole -5- bases.
Preferably, R2 is hydrogen atom, 1- hydroxy-tetrazole -5- bases, more preferably relative to R1 in ortho position or hydroxyl (OH).
More preferable R2 is hydrogen atom.
The corrosion inhibitor of formula (I) can be synthesized according to process well known by persons skilled in the art.See, for example, Tsel
Inski, I.V. et al., Russian Journal of Organic Chemistry, volume 37, the 3rd phase, 2001,430-
Page 436.
For the purpose of description of the invention and appended claims, other than otherwise indicated, dosage, number are expressed
Amount, all numerical value of percentage etc. are understood to use term " about " to modify in all cases.In addition, all ranges include institute
Any combinations of disclosed maximum point and smallest point, and include any intermediate range in it, they may or may not have
Have and specifically enumerates herein.
The cable of the present invention is the cable for power transmission/distribution for including one or more cables core.Preferably, originally
The power cable of invention has three cables core.
In the specification and claims of the present invention, term " cable core " indicates that the inside sequentially contacted each other is partly led
The metal electrical conductor that layer, insulating layer and external semiconductive layer sequentially surround.
Electric conductor in cable of the present invention can be by aluminium, copper or the manufacture of its composite material.The conductor can be metal bar or
The twisted wire-form of metal.
The power cable of the present invention can further comprise metal screen layer and epitheca.
Metal screen layer can be by wire rod, braided fabric, ribbon, the aluminium or copper of the foil form of club or longitudinal sealing
It makes.Single metal screen layer surrounds all cables core in the construction of cable, and each cable core is by it in another construction
Shielded layer surrounds, so that cable has the cable core with metal screen layer as many.
Preferably, the corrosion inhibitor of formula (I) is combined together with support material, forms wherein corrosion inhibitor and by aluminium
The corrosion straining element that manufactured hardware is in direct contact.
For example, the corrosion inhibitor of the formula (I) for cable of the present invention can be absorbed in support material or is adsorbed on
In support material.
The support material for being suitable for the present invention is preferably that chemical/physical is inert to water.
The support material for being suitable for the present invention is preferably heat-resisting at least until 100 DEG C.Advantageously, support material is heat-resisting always
To 150 DEG C, more preferably until 200 DEG C.
The support material for being suitable for the present invention is preferably polymer material, either natural or synthesis.
For example, support material can be cellulose, polyamide or polyester.
Branch can be provided in the various forms for being suitable for cable construction, such as with rope strand, yarn, ribbon or sheet-form
Hold material.
The corrosion inhibitor of formula (I) can by adhesive material, typically polyvinyl alcohol (PVA) or acrylic resin,
It is bonded in support material.Particularly, the solution of support material useful binders material is humidified, then the formula of such as powder type
(I) corrosion inhibitor is sprinkled upon thereon, and is remained trapped in solution, and is captured in adhesive material after drying.
Preferably, the corrosion inhibitor for the formula (I) being in direct contact with hardware made of aluminum to be protected is averaged
Amount ranges are 1 × 10-3g/cm2To 100 × 10-3g/cm2, the surface relative to hardware.
In the cable of the present invention, the corrosion inhibitor for the formula (I) optionally supported in corrosion straining element may be present
In in the metal wire of electric conductor, the interface between conductor and internal semiconductive layer is contacted with metal screen layer, or in metal
The interface of shielded layer and internal semiconductive layer or epitheca.
In the cable of the present invention, barrier can reside in radially outer relative to cable core and metal screen layer
At position.Barrier can be the sheet-form of the longitudinal sealing of metal or plastic/metal layered product.Metal can be aluminium.
In the case of layered product, plastic layer is facing generally towards the external jacket of cable and contacts placement.
In the cable in the present invention with the barrier of aluminous layer, optionally corroding the formula supported in straining element
(I) corrosion inhibitor can contact with this aluminium layer and be existed.
In second aspect, the present invention relates to the methods of production power cable, and the power cable includes made of aluminum
Hardware and corrosion straining element, the corrosion straining element include the support material combined with the corrosion inhibitor of formula (I)：
R1-Ar-R2 (I)
Wherein R1 is 1- hydroxy-tetrazole -5- bases, 2- hydroxy-tetrazole -5- bases, 1- acryloxies-tetrazolium -5- bases or 1-
(2- carboxy vinyls)-tetrazolium -5- bases；
Ar is monocycle or bicyclic aromatic component part；With
R2 is hydrogen atom (H) or 1- hydroxy-tetrazole -5- bases, 2- hydroxy-tetrazole -5- bases, hydroxyl (OH), vinyl, allyl
Base or-O-CO-R4 bases, wherein R4 are the alkenyls for having 2-6 carbon atom,
This method includes the following steps：
With dried forms or then the corrosion inhibitor of the formula (I) dissolved in the polar solvent of evaporation is being sprayed
Support material is spilt, to provide the corrosion straining element；With
Corrosion straining element is set to be in direct contact placement with hardware made of aluminum.
Especially preferred polar solvent is water, acetone and hydroxyl-bearing solvent, such as isopropyl for the method for the present invention
Alcohol and ethyl alcohol.
Advantageously, by the corrosion inhibitor of formula (I) with most 250-300ppmw's (number relative to million weight portions)
Concentration is dissolved in polar solvent.
Preferably, the solution of the corrosion inhibitor of formula (I) is saturated solution in a solvent.
After organic solvent evaporation, the support material of the corrosion inhibitor with formula (I) is entered by payment stations
Into cables manufacturing, this depends on the required position identified in cable.
Brief description
By reading following detailed description with attached drawing in conjunction with reading, it is better understood with the present invention, the detailed description
As example rather than limitation provides, wherein：
Fig. 1 shows the perspective view of power cable according to embodiments of the present invention；
Fig. 2 shows the sections of power cable according to embodiments of the present invention；
Fig. 3 show it is as described in Example 2, it is drawn as time go in the case that with and without corrosion inhibitor
Linear polarization resistance (LPR) variation chart；With
Fig. 4 show it is as described in Example 2, it is drawn as time go in the case that with and without corrosion inhibitor
Corrosion rate variation chart.
Detailed description of the invention
Fig. 1 shows the perspective view of power cable 11 according to embodiments of the present invention.
The power cable 11 of Fig. 1 be the cable of single core and include constitute cable core conductor 12, internal semiconductive layer 13, absolutely
Edge layer 14 and external semiconductive layer 15.Cable core is surrounded by metal screen layer 16 and epitheca 17.
Conductor 12 generally includes metal wire, and the metal wire is preferably manufactured by copper or aluminium, and is compiled by using routine techniques
It is woven in together.
Under selected voltage, the sectional area of conductor 12 is measured with electrical to be conveyed.Electric power electricity according to the present invention
The preferred cross-sections of cable accumulate ranging from 16mm2To 1,600mm2。
Internal semiconductive layer 13, insulating layer 14 and external semiconductive layer 15 are manufactured by polymer material.
Polyolefin, the copolymer of different alkene, alkene and alkene can be selected from by being suitable for the polymer material of layer 13,14 and 15
The copolymer of keyed beta-unsaturated esters, polyester and its mixture.
The example of suitable polymer is：Polyethylene (PE), especially low density PE (LDPE), middle density PE (MDPE) are high
Density PE (HDPE), linea low density PE (LLDPE), ultra-low density polyethylene (ULDPE)；Polypropylene (PP) and its copolymer；
Elastomeric ethylene/propylene copolymer (EPR) or ethylene/propylene/diene hydrocarbon ter-polymers (EPDM)；Ethylene/vinyl ester is copolymerized
Object, such as Ethylene/vinyl acetate (EVA)；Ethene/acrylic ester copolymer, especially ethylene/methyl acrylate (EMA), second
Alkene/ethyl acrylate (EEA) and ethylene/butyl acrylate (EBA)；Ethylene/alpha-olefin thermoplastic copolymer or its mechanical mixture
Object.
In the case of internal semiconductive layer 13 and external semiconductive layer 15, polymer material listed above is added with conductive charcoal
It is black, such as conductive furnace black or acetylene black, to assign polymer material semiconduction energy.
Insulating layer 14, internal semiconductive layer 13 and external semiconductive layer 15 can be manufactured by the thermoplastic material polymerizeing, and be preferably included
The thermoplastic, polymeric materials of the dielectric liquid containing predetermined amount.The example of thermoplastic insulation is disclosed in WO 02/03398, WO 02/
In 27731, WO 04/066318, WO 07/048422 and WO 08/058572.
Metal screen layer 16 is manufactured by metal braid, such as is manufactured from aluminium, and is wound around external semiconductive layer 15.
Epitheca 17 is preferably by polymer material, such as polyvinyl chloride (PVC) or polyethylene (PE) manufacture.
In the implementation of figure 1, the branch of the corrosion inhibitor of formula (I) is carried on the surface towards metal screen layer 16
The corrosion straining element 18 for holding material band forms around metal screen layer 16 and contacts offer.
Similarly, it but is not shown in Fig. 1, preferably with form of yarns in the metal wire of conductor 12, and/or in inside
Between semiconductive layer 14 and conductor 12, and/or corrosion straining element is provided between metal screen layer 16 and external semiconductive layer 15.
Fig. 2 shows another embodiment of the present invention.Fig. 2 elaborates the cable 21 containing three cables core.Each cable
Core includes conductor 22, internal semiconductive layer 23, insulating layer 24 and external semiconductive layer 25.Each cable core is wrapped by metal screen layer 26
It encloses.Epitheca 27 surrounds the cable core of all three shieldings.Each free solid aluminum stick manufacture of conductor 22.
The cables core of three shieldings are twisted and are embedded in filler (or embedded material (bedding)) 29, and the filler (or
Embedded material) it itself is surrounded by epitheca 27.The identical material manufacture that epitheca 27 can be had disclosed by the epitheca 17 of combination Fig. 1.
The material of internal semiconductive layer 23, insulating layer 24, and external semiconductive layer 25 can be directed to class with the cable 11 of Fig. 1 is combined
As cable section those of be already mentioned above it is identical.
In the embodiment of fig. 2, the interface between the conductor 22 of each cable core and internal semiconductive layer 23, provides
The corrosion straining element 28 of the support material band forms of the corrosion inhibitor with formula (I) on the surface towards conductor 22.
Alternatively or additionally, corrosion straining element 28 can have been combined the yarn that positioning is wound described in the cable 11 of Fig. 1
Line or belt shape object.
Similarly, it but is not shown, can be in direct contact with metal screen layer 26 in fig. 2, or in 26 He of metal screen layer
Between external semiconductive layer 25, or corrosion straining element is provided between metal screen layer 26 and epitheca 27.
The cable of the manufacture present invention that can be as disclosed above.Common process unit can be used, in the suitable of manufacturing process
Supply corrosion straining element at step.For example, when corrosion straining element will be located in the wire rod of electric conductor, by form of yarns
Straining element be twisted together with wire rod.For example, when corrosion straining element will be located in electric conductor and protective layer, (insulating layer is interior
Portion's semiconductive layer) between when, yarn or the corrosion straining element of print ribbon form are wound around conductor before squeezing out the layer.
Following embodiments are quasi-, and the present invention is further explained, however is in no way intended to limit the present invention.
Embodiment 1
Synthesize 5- phenyl -1- hydroxyls-(1H)-tetrazolium
Step 1：Prepare N- (2-hydroxybenzoyl) imines chlorine (hydroxybenzimidoyl chloride)
Ethyl alcohol (30mL) is poured over equipped with internal temperature probe, tri- necks of the 250mL circle of reflux condenser and nitrogen inlet
In the flask of bottom.By syringe addition chlorobenzoyl chloride (19.71mL, 23.87g, 0.17 mole), and it is molten to stir during addition this
Liquid.Hydroxy amine hydrochloric acid salt (21.20mL, 35.41g, 0.51 mole) is added in a part, then adds sodium hydroxide 97%
(27.2g, 0.68 mole).Reaction flask is placed in oil bath and is heated 1 hour at 60 DEG C under stiring.It is taken out from oil bath
Flask and stand be cooled to environment temperature.
The mixture is transferred in single neck round-bottom flask, and by rotary evaporation 45 DEG C temperature and 40mbar it is true
The lower concentration of sky.
Solid residue is transferred in separatory funnel, and is extracted with ethyl acetate three times.In Na2SO4Upper dry merging has
Machine layer.Drier is removed by filtration, it is organic in the reduced under vacuum of 45 DEG C of temperature and 40mbar then by rotary evaporation
Layer.
At 5 DEG C, solid residue is recrystallized from 60mL hexanes 2 hours, obtain the crystal of N- (2-hydroxybenzoyl) imines chlorine
(20.21g, 0.13 mole).
Gained reaction yield is 76.9%.
Step 2：Prepare N- (2-hydroxybenzoyl) imido grpup azide
By the sodium azide being dissolved in 10mL water (9.75g, 0.15 mole) equipped with internal temperature probe and reflux condensation mode
It is introduced in the 250mL three neck round bottom of device.N- (2-hydroxybenzoyl) imines chlorine (18.65g, 0.12 mole) is added dropwise in 20mL
Solution in methanol.The solution is placed in oil bath and is heated 2.5 hours at 45 DEG C under stiring.
It is last in reaction, reaction flask is taken out from oil bath and standing is cooled to environment temperature.
The mixture is transferred in single neck round-bottom flask, and by rotary evaporation 25 DEG C temperature and 55mbar it is true
Solvent is distilled under sky.
Solid residue is transferred in separatory funnel, diethyl ether (3 × 30mL) extraction is used in combination three times.With diethyl ether (3 ×
30mL) further extract water phase three times.
With sodium sulphate dry organic layer, filter and evaporate, obtain N- (2-hydroxybenzoyl) imido grpups azide (16.2g,
0.10 mole).
Gained reaction yield is 89.9%.
Step 3：Prepare N- acetoxyl group saccharin base azide
The N- (2-hydroxybenzoyl)s that will be dissolved in 10mL dichloromethane and pyridine (11.85g, 12.12mL, 0.15 mole) are sub-
Amido azide (16.2g, 0.10 mole) is introduced into the 100mL three neck round bottom equipped with internal temperature probe.
The solution is placed in ice/ethanol bath and is maintained at while agitating at 0 DEG C, chloroacetic chloride is then added dropwise
(10.19g, 9.23mL, 0.13 mole).After the addition was complete, the mixture is stirred at room temperature 4 hours.In reaction terminating
Later, it in addition water (20mL) to the mixture, and distills, to remove dichloromethane.
By the filter of folding, obtained solid is filtered, and standing and drying is stayed overnight.It is residual with toluene extraction in separatory funnel
Slag three times (3 × 10mL), removes water, then dries organic layer with sodium sulphate, and filter.Through 2 hours cooling solution to 0 DEG C,
Crystal is obtained, filters the crystal, and 60 DEG C were dried to through 7 hours, obtains N- acetoxyl group saccharin base azide
Crystal (18.36g, 0.09 mole).
Gained reaction yield is 92.3%.
Step 4：Prepare 5- phenyl -1- hydroxyls-(1H)-tetrazolium
The N- acetoxyl group saccharin bases azide (18.36g, 0.09 mole) that will be dissolved in 30mL diethyl ether
It is introduced into the mono- neck round-bottom flasks of 100mL with zinc chloride.Under stiring, it is obtained deacetylated to 20 DEG C through 2 hours cooling solution
Change the cyclisation with intramolecular.After reaction terminating, removed at 30 DEG C of temperature and the vacuum of 400mbar by rotary evaporation
Solvent is removed, 5- phenyl -1- hydroxyls-(1H)-tetrazolium (11.34g, 0.07 mole) crystal is obtained.
Gained reaction yield is 77.7%.
Embodiment 2
Evaluate corrosion-inhibiting energy
Using 5- phenyl -1- hydroxyls-(the 1H)-tetrazolium corrosion inhibitor prepared in embodiment 1, the cable in Fig. 1 is evaluated
The corrosion of aluminium protective layer 16 inhibits in 11.
Using linear polarization resistance (LPR) method of three-electrodes, the corrosion rate under inhibitor presence or absence is evaluated,
Such as in http://www.gamry.com/application-notes/corrosion-coatings/corrosion-
Shown in techniques-polarization-resistance/ like that.
It is used as by using (i) standard Calomel reference electrodes and refers to electrode, (ii) uses the aluminium shielding layer of polyester tape insulation
It is inserted in the diameter 1.6mm with polyester tape insulation between aluminium shielding layer and polyethylene sheath as working electrode (WE), and (iii)
It is used as to electrode (CE) with the aluminum steel of length 45cm, realizes three-electrode systems.
In order to omparison purpose, two systems of the realization with and without corrosion inhibitor.
In the system with corrosion inhibitor, it is immersed in advance containing 0.7mmol/L5- benzene as the aluminum steel to electrode
In base -1- hydroxyls-polymer solution in water of (the 1H)-tetrazolium as corrosion inhibitor (I).In the system without corrosion inhibitor
In, it is immersed in tap water in advance as the aluminum steel to electrode.
Using linear polarization resistance device, typically on the ± 10mV orders of magnitude, polarize the material, relative to open circuit electricity
Gesture.When the potential change of working electrode, induced current is flowed in working electrode and between electrode, and by taking potential to electricity
The slope of flow curve finds the polarization resistance of material.Then this resistance is utilized to find material using Stern-Geary equations
Corrosion rate.
It is shown in FIG. 3 as a result, there is corrosion inhibitor (straight line and filled marks) in abscissa to show
It is drawn in ordinate as the time (hour) passs in the case of without corrosion inhibitor (dotted line and open symbols)
Polarization resistance change (ohmcm2) chart, and in fig. 4 it is shown that go out in abscissa have corrosion inhibitor (dotted line
And diamond indicia) and without in the case of corrosion inhibitor (straight line and circular mark), as the time (hour) passs, indulging
Drawn corrosion rate changes (current density form, μ Amp/cm in coordinate2) chart.
According to fig. 3, the polarization resistance value obtained using the sample with corrosion inhibitor is significantly greater than with without corruption
Those of sample acquisition of corrosion inhibitor.The result shows that the calculating corruption based on LPR methods in the presence of the inhibitors described in Fig. 4
Erosion rate be in the case that there is no inhibitor calculate corrosion rate substantially half.
These results prove that the corrosion inhibitor of formula (I) can effectively inhibit the corrosion of aluminium element in power cable.
Claims (12)
1. a kind of power cable, it includes hardware made of aluminum, wherein corrosion inhibitor is used and hardware
The mode being in direct contact provides, which has the following general formula (I)：
R1-Ar-R2 (I)
Wherein R1 is 1- hydroxy-tetrazole -5- bases, 2- hydroxy-tetrazole -5- bases, 1- acryloxies-tetrazolium -5- bases or 1- (2- carboxylics
Base vinyl)-tetrazolium -5- bases；
Ar is monocycle or bicyclic aromatic component part；With
R2 is hydrogen atom (H) or 1- hydroxy-tetrazole -5- bases, 2- hydroxy-tetrazole -5- bases, hydroxyl (OH), vinyl, allyl
Or-O-CO-R4 bases, wherein R4 are the alkenyls for having 2-6 carbon atom.
2. the power cable of claim 1, wherein when Ar is monocyclic aromatic component part and R2 is different from hydrogen atom, R1 and R2
Relative to each other on o-, m- or p- position.
3. the power cable of claim 1, wherein when Ar is bicyclic aromatic component part and R2 is different from hydrogen atom, R1 and R2
Relative to each other on peri position or the substituent group of identical ring.
4. the power cable of claim 1, wherein corrosion inhibitor have the following general formula (Ia)：
Wherein R1 and R2 has the identical meanings defined with formula (I) in claim 1.
5. the power cable of claim 1, wherein R1 are 1- hydroxy-tetrazole -5- bases and R2 is hydrogen atom.
6. the power cable of claim 1, wherein R2 are hydrogen atom, 1- hydroxy-tetrazole -5- bases, preferably with respect to R1 at ortho position
Upper or hydroxyl (OH).
7. the corrosion inhibitor of the power cable of claim 1, wherein formula (I) is related with support material to inhibit member to be formed to corrode
Part, the wherein corrosion inhibitor are in direct contact with the hardware being manufactured from aluminium.
8. the power cable of claim 7, wherein corrosion inhibitor are absorbed in support material or are adsorbed in support material.
9. the power cable of claim 1, wherein the corrosion inhibitor for the formula (I) being in direct contact with the hardware being manufactured from aluminium
Average dose be 1 × 10-3g/cm2To 100 × 10-3g/cm2, the surface relative to hardware.
10. a kind of method producing power cable, the power cable includes that the hardware being manufactured from aluminium and corrosion inhibit member
Part, the corrosion straining element include the support material for the corrosion inhibitor for being combined with formula (I),
R1-Ar-R2 (I)
Wherein R1 is 1- hydroxy-tetrazole -5- bases or 2- hydroxy-tetrazole -5- bases；
Ar is monocycle or bicyclic aromatic component part；With
R2 is hydrogen atom (H) or 1- hydroxy-tetrazole -5- bases, 2- hydroxy-tetrazole -5- bases, hydroxyl (OH), vinyl, allyl
Or-O-CO-R4 bases, wherein R4 are the alkenyls for having 2-6 carbon atom；
This method includes the following steps：
With dried forms or the corrosion inhibitor of the formula (I) dissolved in the polar solvent of evaporation is then being sprayed into branch
Material is held, to provide the corrosion straining element；With
So that corrosion straining element is in direct contact with hardware made of aluminum and places.
11. the method for claim 10, wherein polar solvent are selected from water, acetone and hydroxyl-bearing solvent.
12. the method for claim 10, wherein by corrosion inhibitor with most 250-300ppmw (relative to million weight portions
Number) concentration be dissolved in polar solvent.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/EP2015/072081 WO2017050387A1 (en) | 2015-09-25 | 2015-09-25 | Power cable of aluminium coated with a tetrazole compound corrosion inhibitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108350583A true CN108350583A (en) | 2018-07-31 |
| CN108350583B CN108350583B (en) | 2020-09-08 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201580083236.9A Active CN108350583B (en) | 2015-09-25 | 2015-09-25 | Aluminum power cable coated with tetrazolium compound corrosion inhibitor |
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| Country | Link |
|---|---|
| US (1) | US10217546B2 (en) |
| EP (1) | EP3353334B1 (en) |
| CN (1) | CN108350583B (en) |
| AU (1) | AU2015410274B2 (en) |
| BR (1) | BR112018005361B1 (en) |
| ES (1) | ES2837150T3 (en) |
| WO (1) | WO2017050387A1 (en) |
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| FR3113979A1 (en) * | 2020-09-04 | 2022-03-11 | Nexans | Electric cable limiting partial discharges |
| IT202000032015A1 (en) * | 2020-12-23 | 2022-06-23 | Prysmian Spa | MEDIUM VOLTAGE ELECTRIC CABLE WITH BETTER FIRE BEHAVIOR |
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|---|---|---|---|---|
| EP1457996A2 (en) * | 2003-03-13 | 2004-09-15 | Servicios Condumex S.A. De C.V. | Dry water-resistant coaxial cable and manufacturing method of the same |
| CN1897172A (en) * | 2000-04-20 | 2007-01-17 | 北卡罗来纳州克门斯扣普有限公司 | Corrosion-protected coaxial cable, its production method and andcorrosion-inhibiting composition |
| CN104094364A (en) * | 2011-12-23 | 2014-10-08 | 普睿司曼股份公司 | Cable comprising an element indicating water infiltration and method using said element |
| US20150152329A1 (en) * | 2013-12-02 | 2015-06-04 | Ecolab Usa Inc. | Tetrazole based corrosion inhibitors |
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| US4873139A (en) | 1988-03-29 | 1989-10-10 | Minnesota Mining And Manufacturing Company | Corrosion resistant silver and copper surfaces |
| JP2902281B2 (en) | 1993-11-24 | 1999-06-07 | 千代田ケミカル株式会社 | Water-soluble metal corrosion inhibitor |
| DE60102817T2 (en) | 2000-06-28 | 2004-09-30 | Pirelli & C. S.P.A. | CABLE WITH RECYCLABLE SHEATHING |
| EP1323171B1 (en) | 2000-09-28 | 2004-12-15 | Pirelli & C. S.p.A. | Cable with recyclable covering |
| US6824815B2 (en) * | 2000-12-27 | 2004-11-30 | Pirelli Cavi E Sistemi S.P.A. | Process for producing an electrical cable, particularly for high voltage direct current transmission or distribution |
| US6903263B2 (en) * | 2000-12-27 | 2005-06-07 | Pirelli, S.P.A. | Electrical cable, particularly for high voltage direct current transmission or distribution, and insulating composition |
| WO2004066317A1 (en) | 2003-01-20 | 2004-08-05 | Gabriele Perego | Cable with recycable covering layer |
| US6858805B2 (en) * | 2003-05-08 | 2005-02-22 | Commscope Properties Llc | Cable with foamed plastic insulation comprising and ultra-high die swell ratio polymeric material |
| DE602005021712D1 (en) | 2005-10-25 | 2010-07-15 | Prysmian Spa | ENERGY CABLE WITH A DIELECTRIC FLUID AND A MIXTURE OF THERMOPLASTIC POLYMERS |
| CA2669741C (en) | 2006-11-15 | 2014-02-04 | Prysmian S.P.A. | Energy cable |
| US20100288528A1 (en) * | 2009-05-14 | 2010-11-18 | Commscope, Inc. Of North Carolina | Coaxial cables having low bond precoat layers and methods of making same |
-
2015
- 2015-09-25 BR BR112018005361-9A patent/BR112018005361B1/en active IP Right Grant
- 2015-09-25 AU AU2015410274A patent/AU2015410274B2/en active Active
- 2015-09-25 WO PCT/EP2015/072081 patent/WO2017050387A1/en active Application Filing
- 2015-09-25 EP EP15771568.1A patent/EP3353334B1/en active Active
- 2015-09-25 US US15/760,791 patent/US10217546B2/en active Active
- 2015-09-25 ES ES15771568T patent/ES2837150T3/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1897172A (en) * | 2000-04-20 | 2007-01-17 | 北卡罗来纳州克门斯扣普有限公司 | Corrosion-protected coaxial cable, its production method and andcorrosion-inhibiting composition |
| EP1457996A2 (en) * | 2003-03-13 | 2004-09-15 | Servicios Condumex S.A. De C.V. | Dry water-resistant coaxial cable and manufacturing method of the same |
| CN104094364A (en) * | 2011-12-23 | 2014-10-08 | 普睿司曼股份公司 | Cable comprising an element indicating water infiltration and method using said element |
| US20150152329A1 (en) * | 2013-12-02 | 2015-06-04 | Ecolab Usa Inc. | Tetrazole based corrosion inhibitors |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2015410274A1 (en) | 2018-04-26 |
| WO2017050387A1 (en) | 2017-03-30 |
| BR112018005361A2 (en) | 2018-10-09 |
| US20180254123A1 (en) | 2018-09-06 |
| NZ741172A (en) | 2023-10-27 |
| EP3353334B1 (en) | 2020-09-23 |
| EP3353334A1 (en) | 2018-08-01 |
| AU2015410274B2 (en) | 2022-02-03 |
| CN108350583B (en) | 2020-09-08 |
| US10217546B2 (en) | 2019-02-26 |
| BR112018005361B1 (en) | 2022-07-26 |
| ES2837150T3 (en) | 2021-06-29 |
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